Polyarcrylonitrile basic dyeing process with anionic assistant

ABSTRACT

WHEREIN R represents an alkyl or alkylene radical with 7 to 21 carbon atoms, A is the group -COO- or -OCO-, B is a mono- or binuclear aromatic radical, R1 represents hydrogen, hydroxyl, alkyl, alkoxy, cycloalkyl, aryl, aralkyl or halogen and M is an inorganic or organic cation. The assistants display a good retardation and levelling action without the occurrence of blocking effects. The dyed material is levelly dyed in light and dark shades and show good fastness properties.   A process for dyeing polyacrylonitrile textile materials with basic dyes in acid aqueous dyeing baths is provided. The process is carried out in the presence of anionic assistants of the formula

' Unite States Patent [1 1 Haase Dec. 9, 1975 POLYARCRYLONITRILE BASIC DYEING PROCESS WITH ANIONIC ASSISTANT [44] Published under the Trial Voluntary Protest Program on January 28, 1975 as document no. B 314,489.

[30] Foreign Application Priority Data Dec. 21, 1971 Switzerland 18720/71 [52] US. Cl. 8/169; 8/173; 8/179 [51] Int. Cl. D06P 5/04 [58] Field Of Search 8/89, 173, 177 AB, 169

[56] References Cited UNITED STATES PATENTS 2,133,288 10/1938 Flett 8/89 X 2,250,098 7/1941 I-Iardt et al 8/89 X 2,310,074 2/1943 Gotte 8/54 3,164,566 1/1965 Horn 8/173 X 3,451,762 6/1969 Hendricks et a1 8/89 X 3,619,122 11/1971 DeMaria 8/173 3,619,123 11/1971 Waiz 8/173 3,687,603 8/1972 Abel et a1. 8/173 X 3,713,768 l/l973 Wegmuller et a1. 8/173 X 3,718,428 2/1973 Streck 8/173 3,765,835 10/1973 Clarke et a1. 1 1 1 8/173 X 3,775,056 1l/1973 Grossmann et a1. 8/173 X FOREIGN PATENTS OR APPLICATIONS 1,355,971 4/1963 France 1,938,227 2/1971 Germany OTHER PUBLICATIONS Chem. Abstracts, Vol. 48, (1954), Column 1711 i.

Primary ExaminerBenjamin R. Padgett Assistant Examiner-P. A. Nelson Attorney, Agent, or FirmJoseph G. Kolodny; Edward McC. Roberts; Prabodh I. Almaula [57] ABSTRACT A process for dyeing polyacrylonitrile textile materials with basic dyes in acid aqueous dyeing baths is provided. The process is carried out in the presence of anionic assistants of the formula -R B 1 MG) wherein R represents an alkyl or alkylene radical with 7 to 21 carbon atoms, A is the group COO or OCO, B is a monoor binuclear aromatic radical, R represents hydrogen, hydroxyl, alkyl, alkoxy, cycloalkyl, aryl, aralkyl or halogen and M is an inorganic or organic cation. The assistants display a good retardation and levelling action without the occurrence of blocking effects. The dyed material is levelly dyed in light and dark shades and show good fastness properties.

24 Claims, No Drawings POLYARCRYLONITRILE BASIC DYEING PROCESS WITH ANIONIC ASSISTANT The present invention provides a process for dyeing textile fibre material made from polyacrylonitrile with basic dyes in acid, aqueous dyeing preparations. The process consists in using as dyeing assistant anionic compounds of the formula --A"IEB R Tao wherein R represents an alkyl or alkylene radical with 7 to 21 carbon atoms, A represents the group COO or OCO-, B represents a monoor binuclear aromatic radical, R represents a hydrogen atom, a hydroxyl group, an alkyl, alkoxy, cycloalkyl, aryl or aralkyl radical or a halogen atom, and M represents an inorganic or organic cation. B may be, for example, a benzene, naphthalene or diphenyl radical. R is, for example, a methyl, ethyl, propyl, amyl, decyl, methoxy, ethoxy or also a hydroxybutyl, hydroxyamyl or hydroxydecyl radical, also a cyclopentyl or cyclohexyl radical or a phenyl or benzyl radical, and furthermore too a chlorine, bromine or iodine atom.

Preferably, the anionic compounds correspond to the formula wherein R represents an alkyl or alkylene redical with 11 to 18 carbon atoms, A represents the group COO or OCO--, B represents a benzene, naphthalene or diphenyl radical, R represents a hydrogen atom, an alkyl or alkoxy radical with l to carbon atoms, a 5- or 6-membered cycloalkyl radical, a benzyl or phenyl radical or a halogen atom, and M represents an inorganic or organic cation.

Particularly suitable anionic compounds correspond to the formulae wherein R and M have the indicated meanings and R is a hydrogen atom, an alkyl or alkoxy radical with 1 to 4 carbon atoms, preferably a methyl or methoxy group, or is a chlorine or bromine atom.

The radicals R and R are alkyl and alkylene radicals which may be straight chain or branched, substituted or unsubstituted. Examples of suitable substituents are halogen atoms or low molecular alkyl radicals with l to 4 carbon atoms. Particularly suitable radicals R and R are the hydrocarbon radicals of' corresponding saturated and unsaturated fatty acids or fatty alcohols, e.g., the radicals of caprylic, capric, lauric, myristic, palmitic, stearic, arachidic, behenic, decenoic, dodecenoic, tetradecenoic, hexydecenoic or oleic acid. It is also possible to use radicals of polyunsaturated fatty acids, for example those of linoleic or linolenic acid.

M is an organic or preferably an inorganic cation. Preferred inorganic cations are those of the alkali metal group, e.g., the lithium, but especially sodium and potassium cation, but also the ammonium ion. As organic cations there are used, for example, derivatives of organic amines which contain at least one protonised nitrogen atom, primary, secondary and tertiary monoand polyamines which are optionally further substituted being suitable.

Mention may be made of mono-, diand trialkanolamines, for example the ethanolamines.

The anionic compounds contain preferably at most two mononuclear aromatic radicals which occur independently in the molecule or also, it condensed, form a single binuclear radical. If, for example, B and B are benzene radicals, R and R may be phenyl or aralkyl radicals with up to 10 carbon atoms; but if they are naphthalene radicals, then R, and R should preferably not be aromatic radicals.

Particular interest attaches to the compounds of the formulae (7) 9 6) n 2n+l or C H COO Also suitable are compounds of the formulae 3 and of the formulae so (3 n 3 1 C H OCO C H CO so (9 M 9 c n oco so 3 M1 (+3 und c n ocmw so 3 9 M G9 In the formulae (7) to 14), R represents a hydrogen atom or a methyl or methoxy group, M represents sodium, potassium or protonised mono-, dior triethanolamine and n represents a number from 11 to 18.

In the componds of the formulae (7) to (9) and (1 1), the S0 M group is usually in B-position to the CO0 and OCO group and R is preferably a hydrogen atom. A substitution in the orthoor meta-position is also possible.

The manufacture of the anionic compounds used for the present invention is known and is carried out e.g. by reacting fatty acid derivatives with corresponding phenolic or naphtholic compounds, or by reacting fatty alcohols with benzene or naphthalene derivatives which contain carboxylic acid groups or substituents which can be converted into such groups.

The amount of anionic assistant in the dyeing preparations is for example 0.1 to 5 percent, and preferably 1 to 3 percent, relative to the fibre material to be dyed.

The dyeing is carried out in liquors which have pH values of about 3 to 6, preferably 3.5 to 5. The pH values are adjusted with mineral acids, or preferably with lower organic acids, such as formic, acetic, oxalic or tartaric acid. Furthermore, it is advantageous to dye in buffered liquors, i.e., mixtures of acids with corresponding salts.

As basic dyes the dyestuff preparation according to the invention preferably contains the customary salts and metal halide (preferably zinc chloride) double salts of the known cationic dyes, in particular the methine or azomethine dyes, which contain the indolinium, pyrazolium, imidazolium, triazolium, tetrazolium, oxdiazolium, thiodiazolium, oxazolium, thiazolium, pyridinium, pyrimidinium, or pyrazinium ring. The cited heterocycles can be substituted and/or condensed with aromatic rings. Also possible are cationic dyes of the diphenylmethane, triphenylmethane, oxazine and triazine series, and finally, dye salts of the arylazole and anthraquinone series with external onium group.

It is also possible to use dyestuff mixtures. The amount of dye is about 0.5 to 5 percent, relative to the fibre material to be dyed.

The dyeing preparations can contain further assistants which are conventionally used in dyeing, for example non-ionic surface active compounds, in particular addition products of ethylene oxide and alcohols, phenols and amines, or organic solvents, in particular ethylene glycol monoethyl ether or thiodiethylene glycol, as well as ethylene carbonate.

The dyeing process according to the invention can be applied to all acrylic or modacrylic textile materials, i.e., to all textile materials whose fibres are composed of homopolymers or copolymers in which acrylonitrile predominates. Copolymers are for example those of acrylonitrile and other vinyl compounds, such as acrylic esters, acrylic amides, vinyl pyridine, vinyl chloride, vinylidene chloride, copolymers of dicyanoethylene and vinyl acetate, as well as of acrylonitrile block copolymers.

The fibre material can be dyed according to the invention in any desired form, for example as flocks, spinning cables, worsted tops, yarn, woven or knitted fabrics. The textile material is dyed by means of known processes, preferably by the exhaust method, in dyeing machines and vessels suitable for the purpose, both under normal pressure and in sealed vessels under pressure.

The dyeing preparation according to the invention is appropriately manufactured by making the basic dye into a paste with the amount of acid or buffer salt acid to be used, pouring hot water on to the paste and then treating the resulting dye bath with the anionic assistants as well as, optionally, further assistants conventionally used in dyeing. The preparations possess good stability.

The textile material is put into this liquor, which can have a temperature of from 50 to C, and then optionally the temperature of the liquor is increased in order to dye in the temperature range of from 80 to C, preferably at the boiling point of the liquor.

The liquor ratios are about 1:10 to 1:50, preferably 1:20 to 1:40. The dyed material is subsequently washed and dried in the customary manner.

Dyeings of excellent levelness and good fastness properties are obtained with the process according to the invention for dyeing textile material made from polyacrylonitrile accompanied by the use of anionic assistants. In particular, when dyeing with a mixture of different basic dyes no selectively dyed patches of fibre are obtained, i.e., the anionic assistants display a good retardation and levelling action without the occurrence of blocking effects. Furthermore, no alteration of shade occurs during the dyeing process. And, in addition, good exhaustion of the liquor is observed. In the process according to the invention, and with the use of the dyeing preparations according to the invention, it is possible to dye light and dark shades levelly and fast independently of the rates of absorption of the dyes or the properties of the substrates, e.g., their chemical composition.

The following Examples will serve to illustrate the invention, but without being in any way limitative thereof. The parts and percentages are by weight unless otherwise stated.

EXAMPLE 1 A fabric made from polyacrylonitrile (25 g) is put at 60C into a litre of dye liquor which contains 0.125 g of a dyestuff mixture consisting of: 25 parts of the dyestuff of the formula 65 parts of the dyestuff of the formula CHO S 3.2 g of glacial acetic acid, ml of 10% aqueous sodium hydroxide solution, and 0.2 g of the assistant of the formula C H COO $0 in solution. The temperature of the dyebath is raised to boiling point and dyeing is carried out for 1 hour at this temperature. The material dyed in this way is thereupon rinsed with lukewarm and cold water and dried. A uniform bluish grey dyeing is obtained under these conditions. No alteration of shade is observed during the dyeing.

The anionic assistant mentioned hereinabove is manufactured, for example, in the following way: 53 g of potassium-4-phenolsulphonate and 79 g of oleic acid C IN t ram. I 24 chloride are kept at to C for 20 hours in 20 ml of xylene, while stirring. The reaction mixture is cooled to about 1 10C, then diluted with 400 ml of ligroin, and filtered hot. The solvent is subsequently distilled off in vacuo and the residue is stirred once more with 300 ml 3 of ethyl acetate: alcohol (1:1) and filtered. The filter residue is washed with petroleum ether and dried in vacuo, to give 49.6 g of the water-soluble product of the formula e r1 co0 803K The assistants listed in the following Table were obtained in similar manner.

Instead of the anionic assistant it is also possible to use with equal results those of the following Table I in the given amounts.

Table I Assistant g /1 liquor (106) C l-l COO- radical of coconut acid so 1 -o,5

oil fatty I Table l-Continued Assistant g [1 liquor COOC S O K H 118) C H -COO 9 33 SO Hl} bll2Crl2OH 0,25

IC-B 9 6 (11} c n coo so r 1\cH cH on 0,25

CH CH QH (120i H COO so' @YLCHZCHZOH 0 25 H b CH CH OH EXAMPLE 2 3,2 g of glacial acetic acid, ml of 10 percent aqueous A fabric made from Polyac ylonitrile g) is put at 40 igg g gg gg f and g of the asslstant of 60C into a litre of dye liquor which contains 0.325 g of the dyestuff of the formula The temperature of the dye bath is raised to the boiling point and the bath is kept at this temperature for l (121) O N I hour. The dyed material is rinsed in the usual way with 2 lukewarm water and dried. A uniform, red dyeing is obtained.

c H CH 2 5 3 N N- CH CH 3 v 4 Similarly good dyeings are produced on polyacryloni- Z 5 3 trile fibres by using 0.325 g of the following dyes and observing the conditions described hereinabove:

Table II Shade on y Dye polyac rylor nitrile f "i hvn q O NH 3 122 a S CH CH N Cl-l Cl blue CH 0 o Table II Continued Shade on Dye pQlyacr-ylonitrile fibres 3 CII--CH CH CH C1 23 l N C CH CH N\ Cl red I CH CH CH 3 F c-cn 3 N 124 E I N 3 yellow S CH r l v (CH N CH OC -N N (5 Cl yellow H CC 126 blue 3 80 C11 HNOCH CH N (c 11 2 blue -11 0 5 4 b cu 2 CH -H C Table II Co'r tinued Shade on poly- D acrylonitrile ye fibres H C /CH n o b l 4 f lue H O C v CH 20 EXAMPLE 3 R A modified polyacrylonitrile fabric containing car- 1 boxyl groups (25 g) is put at 98C into a litre of dye li- R A B M quor which contains 0.25 g of a dyestuff mixture con- SO sisting of: 44 parts of the dyestuff of the formula 25 3 H C /CH C C CH CH I (14 -NH OCH Cl 12 parts of the dyestuff of the formula wherein R is an alkyl or alkylene radical with 7 to 21 c N (146) u n 7 N\ c-N-NN 01 I c 11 ca 44 parts of the dyestuff of the formula carbon t m A i the group -CO O or O- N r 4 3 c N-N- N Q 2 c1 U It 011 0 I 3 0.2 g of glacial acetic acid and 0.5 g of the assistant of the formula (104). Dyeing is carried out at this temperature for 1 hour and the goods are then rinsed and dried in the usual manner. A level grey dyeing is obtained with impeccable build-up of shade.

I claim:

1. A process for dyeing textile fibre material made from polyacrylonitrile, comprising the step of treating the fibre material with a basic dye in an acidic, aqueous preparation, which further comprises as dyeing assistant an anionic compound of the formula CO-, B is benzene, naphthalene or diphenyl, R is hydrogen, hydroxyl, alkyl, hydroxyalkyl, alkoxy, cycloalkyl aryl, aralkyl or halogen, and M represents an inorganic or organic cation.

2. A process of claim 1, wherein the anionic compound is of the formula wherein R is alkyl or alkylene with 11 to 18 carbon atoms and R represents hydrogen, alkyl or alkoxy containing 1 to 10 carbon atoms, or halogen 3. A process of claim 1, wherein R is hydroxyl.

4. A process according to claim 2, wherein the anionic compounds is of the formula wherein R is hydrogen, alkyl or alkoxy containing 1 to 4 carbon atoms, or chlorine or bromine.

5. A process of claim 2, wherein the anionic compound is of the formula SO36 M Rg- OCO wherein R is hydrogen, alkyl or alkoxy containing 1 to 4 carbon atoms, or chlorine or bromine.

6. A process of claim 2, wherein the anionic compound is of the formula in which R, is hydrogen, alkyl or alkoxy containing 1 to 4 carbon atoms, or is chlorine or bromine.

7. A process of claim 2, wherein the anionic compound is of the formula so M R2- COO pound is of the formula wherein R represents hydrogen, chlorine or bromine or methyl or methoxy, M represents sodium, potassium, protonised mono-, dior triethanolamine, and n represents a whole number from 11 to l8.

11. A process of claim 10, wherein the anionic compound is of the formula (9 c n 00 o so M 22 12. A process of claim 5, wherein the anionic compouridis of the" formula wherein R represents hydrogen, chlorine or bromine or methyl or methoxy, M represents sodium, potassium, protonised mono-, dior triethanolamine and n represents a whole number from 11 to 18, and the -SO M group is in the metaor ortho-position to the CO-O group.

13. A process of claim 6, wherein the anionic compound is of the formula wherein M represents sodium, potassium, protonised mono-, dior triethanolamine, and n represents a whole number from 11 to 18.

14. A process of claim 8, wherein the anionic compound is of the formula wherein M represents sodium, potassium, protonised mono-, di or triethanolamine, and n represents a whole number from 11 to 18.

15. A process of claim 1, wherein the anionic compound is used in amounts of from 0.1% to 5% relative to the fiber material.

16. A process of claim 15, wherein the treatment is carried out with a preparation which has a pH of 3 to 6.

17. A process of claim 16, wherein the treatment is carried out with a buffered preparation.

18. A process of claim 15, wherein the treatment is carried out by the exhaust method.

19. An acid aqueous dyeing preparation which contains at least one basic dye and an anionic compound of the formula RA B M R2A B M wherein R is an alkyl or alkylene radical with 11 to 18 carbon atoms, A is the group CO-O- or OCO,

R is hydrogen, alkyl or alkoxy with 1 to carbon the anionic compound is used. atoms, or halogen, and M is an inorganic or organic 23. A process of claim 16, wherein the preparation cation. has a pH value of 3.5 to 5.

21. A preparation of claim 19, which has a pH of 3 to 5 24. A preparation of claim 21, which has a pH of 3.5 to 5.

22. A process of claim 15, wherein 1 t0 3 percent of 

1. A PROCESS FOR DYEING TEXTILE FIBRE MATERIAL MADE FROM POLYACRYLONITRILE, COMPRISING THE STEP OF TREATING THE FIBRE MATERIAL WITH A BASIC DYE IN AN ACIDIC, AQUEOUS PREPARATION, WHICH FURTHER COMPRISES AS DYEING ASSISTANT AN ANIONIC COMPOUND OF THE FORMULA
 2. A process of claim 1, wherein the anionic compound is of the formula
 3. A process of claim 1, wherein R1 is hydroxyl.
 4. A process according to claim 2, wherein the anionic compounds is of the formula
 5. A process of claim 2, wherein the anionic compound is of the formula
 6. A process of claim 2, wherein the anionic compound is of the formula
 7. A process of claim 2, wherein the anionic compound is of the formula
 8. A process of claim 1, wherein the inorganic cation is a sodium, potassium or ammonium ion.
 9. A process of claim 1, wherein the organic cation is a derivative of an organic amine which contains at least one protonised nitrogen atom.
 10. A process of claim 4, wherein the anionic compound is of the formula
 11. A process of claim 10, wherein the anionic compound is of the formula
 12. A process of claim 5, wherein the anionic compound is of the formula
 13. A process of claim 6, wherein the anionic compound is of the formula
 14. A process of claim 8, wherein the anionic compound is of the formula
 15. A process of claim 1, wherein the anionic compound is used in amounts of from 0.1% to 5% relative to the fiber material.
 16. A process of claim 15, wherein the treatment is carried out with a preparation which has a pH of 3 to
 6. 17. A process of claim 16, wherein the treatment is carried out with a buffered preparation.
 18. A process of claim 15, wherein the treatment is carried out by the exhaust method.
 19. An acid aqueous dyeing preparation which contains at least one basic dye and an anionic compound of the formula
 20. A preparation of claim 19, which contains an anionic compound of the formula
 21. A preparation of claim 19, which has a pH of 3 to
 6. 22. A process of claim 15, wherein 1 to 3 percent of the anionic compound is used.
 23. A process of claim 16, wherein the preparation has a pH value of 3.5 to
 5. 24. A preparation of claim 21, which has a pH of 3.5 to
 5. 